DE1769156A1 - Styryl dyes - Google Patents

Description

PATENT LAWYERS
DR -.- ING. H. FINCKE DIPL.-ING. H. BOHR DIPL-ING. S. STAEGER

Remote call: »26 60« 0

8 MÜNCHEN 5, MOIlerstrafie 31

April 11, 1968

Folder 21626 - Dr.K ..
Case D.20132 / 2040 ^ / 20741

description

to the patent application of

IMPERIAL CHEMICAL INDUSTRIES LTD. ',, London, Great Britain

concerning:

PRIORITIES

"Styryl dyes"

: 12.4 * 1967, 27 * 7 * 1967, December 29, 1967, 26, J. 1968 Great Britain

The invention relates to novel dyes and re insbesonde- Λ to new water-insoluble dyes in the dyeing of synthetic textile materials of value.

According to the invention are water-insoluble styryl dyes suggested that aind free of sulfonic acid groups and the formula

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CN

Η '

own what

Z represents hydrogen, chlorine, bromine, lower alkyl or lower alkoxy;

R represents an optionally substituted lower alkyl radical;

m is 2 or 3;

η is 1 or 2; and

Y is an acyloxy, urethane or an optionally substituted one Represents alkoxy, aryloxy or aralkoxy group.

In this specification the term "lower alkyl" means or "lower alkoxy" alkyl and alkoxy groups containing 1 to 4 carbon atoms.

As examples of lower alkyl * and lower alkoxy groups, those represented by Z should be mentioned: ethyl, a-propyl, η-butyl, ethoxy, n-bromopoxy, n-butoxy and above especially methoxy and methyl.

109839/1 34A

Examples of radicals represented by R should be earthed: methyl, ethyl, n-propyl and n-butyl and substituted derivatives of these radicals, for example hydroxy, lower alkoxy and cyano derivatives, in particular δ-hydroxyethyl , ä-Methoxyäthyl-, ü- or jr-Äthoxypropyl-, a ^ yanoäthyl- and a- or Ifs-Oyanopropprlradikal " * .b " however, it is preferred that R represents the methyl radical.

It is further preferred that η be 1 and that m be the same 2 is

. ■ ■ <

The acyloxy groups represented by Y are vofsugswelee groups of the formula: X.CO.O- or X.8O ₂ O-, where X is an optionally substituted carbon hydrogen radical, in particular an optionally substituted lower alkyl or monocyclic aryl radical. The urethane groups represented by Y are preferably groups of the formula: X.MHCOO-, where X has the specified * meaning. Specific examples of radicals represented by X should be mentioned: methyl, ethyl, n-propyl, η-butyl, fl-hydraethyl, β-cyanoethyl, i-methoxyethyl, β- or γ-ethoxypropyl, hienyl , Chlorophenyl, tolyl, methoxyphenyl, nitrophenyl, carbomethoxyphenyl, carboethoxyphenyl, and B-hydroxyethoxypheuyl.

10 9 8 3 9/13 4 4

Υ is preferably a phenoxy * · · or benzoyloxy which is substituted by chlorine, lower alkyl, lower alkoxy, nitro or Carboniedrigalkoxy.

The optionally substituted alkoxy, aryloxy or aralkoxy groups, represented by Y are preferably unsubstituted or substituted half-alkoxy, monocyclic Aryloxy or monocyclic aryl lower alkoxy groups, e.g. Methoxy, ethoxy, n-propoxy, n-butoxy, ß-hydroxyäfchoxy, ß-methoxyethoxy, ß-ethoxyethoxy, fl-cyanaethoxy, benzyloxy, phenoxy, tolyloxy, Chlorophenoxy, nitrophenoxy, bromophenoxy, carbomethoxyphenoxy and carboethoxyphenoxy.

In accordance with another feature of the invention, a method proposed for the preparation of the above-described water-insoluble styryl dyes, which is carried out in that one an aldehyde of the formula

CHO

Formula I.

wherein R ₁ Z, Y, m and η have the meanings given above, reacts with malononitrile.

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The process according to the invention is expediently carried out by converting the reactants together in an organic solvent such as methanol, and in the presence of a basic compound such as ammonia or a secondary amine, for example diethylamine or piperidine, or an alkali metal derivative of an alcohol, for example The sodium derivative of methanol or ethanol is stirred, the reaction being carried out at a temperature between 20 ^° C. and the boiling point of the organic solvent. The dye obtained in this way is then isolated by conventional methods, for example by iteration of the precipitated solid or by removing the organic solvent by distillation or by adding a liquid such as, for example, water, which precipitates the dye from the organic solvent. J-

The aldehydes of the formula I can for their part be obtained in this way «Ground that you have the appropriately substituted aniline of the formula

treated with hexamethylenetetramine in ethanol, a mixture of

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Acetic acid and formic acid are added, and the resulting product with a dilute aqueous solution of hydrochloric acid hydro * lysed *

According to a further feature of the invention, another Process for the preparation of the styryl dyes according to the invention, where Y represents a urethane group, suggested which is carried out by an isocyanate with a compound of the formula

Z HO Z ^ fY

Formula II

converts, in which R, Z, m and η have the meanings given be ~ sit·

This other process can expediently be carried out by placing the reaction participants together in an inert organic liquid, such as SoB. Toluene, preferably at a temperature between 15 ⁰ C and the boiling point of the inert organic liquid, is stirred. The resulting dye can then be isolated by conventional methods.

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Ala examples of isocyanates which can be used in this process should be mentioned s phenyl isocyanate, methyl isocyanate, and p-nitrophenyl isocyanate.

Compounds of the formula II can in turn be obtained in this way be that you malononitrile with an aldehyde of the formula

_. . .. -OHO

OR

in methanol and in the presence of a basic catalyst.

According to a further feature of the invention, another _ Process for the preparation of the styryl dyes of the invention, in which Y represents an acyloxy group, suggested which is carried out in that a compound of the formula II treated with an acylating agent "

This further method according to the invention can be expedient be carried out by having the reaction ons participants together in a basic solvent, such as ", B. Pyridine,

10983 δ / 134 4

or in an inert organic liquid, such as toluene, which contains a basic liquid, stirs · The resulting Color to ff can then easily be isolated by traditional methods "earth.

The acylating agents which are used in the process of the invention are usually the acid chloride or anhydrides " the corresponding acid. Examples for acylating agents bind; Acetyl chloride, acetic acid anhydride, benzoyl chloride, methane sulfonyl chloride, renzolaulfonyl chloride, p-toluenesulfonyl chloride, Methoxybenaoylchloride, Nitrobenzoylchloride, Chlorbencoylchlorld, Carbomethoxybenoyl chloride and carbonethoxyben-koleulfonyl chloride.

A preferred class of styryl dyes similar to the invention form the dyes of the formula

Y-

CH ₂ CH ₂

wherein γ and Z have the meanings given.

The dyes of this class have excellent build-up properties on aromatic polyester textile materials; in this

ORIGINAL 109839/1344

In particular, the dyes of this preferred class in which Y is an optionally substituted one Represents phenoxy or ßenzoyloxy radical

The above-mentioned dyes are also synthetic dyes Textile materials of value, for example cellulose acetate textile materials, such as secondary cellulose acetate and cellulose triacetate textile material! · ^ Polyamide text !! materials, such as polyhexaethylene adipamide textile materials, and preferably aromatic polyether textile materials, such as polyethylene terephthalate textile materials, such as textile materials can be used in fora Threads, yarns or woven or knitted fabrics are present.

Sole textile materials can expediently be dyed with the dyes defined above by immersing the textile materials in a dyebath which contains an aqueous dispersion of one or more of the dyes mentioned, the dye bath preferably being a nonionic, cationic and contains / or anionic surfactant, and dad to the dyebath for a specified time at a suitable temperature heated "in the case of secondary Celluloseacetattextilmaterialien it is preferred aussu- the dyeing process at a temperature in the range between 60 and 85 ⁰ C.

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to lead; in the case of cellulose triacetate or τοη Polyaaidtextilmaterialien ea is preferable that the dyeing process at 95 - 100 ⁰ C to carry out; in the case of aromatic Polyestertextilmateriallen the dyeing process can either be "wipe 90 and 10O ⁰ O (preferably using a carrier such as diphenyl barren o-Hydroxydlphenyl is present), or at a temperature above 100 ⁰ C, preferably at a temperature" at a temperature wipe 120 - 140 ⁰ C, under superatmospheric pressure.

Alternatively, the aqueous dispersion of the dye mentioned can be used on the textile material by soldering or printing processes and on final heating or damping of the textile material · can be applied. Such a procedure avoids ea Thickeners, such as gum tragacanth, gum arabic or sodium alginate, in the aqueous dispersion of the color mentioned. to incorporate substances.

At the end of the dyeing process, precautions are taken not to rinse the dyed textile material in water or to briefly soak it; before the dyed textile material is finally dried. In the case of an aromatic polyester fabric, it is also preferred to use the dyed fabric a treatment in an alkaline aqueous solution of

ORIGINAL INSPECTED

109839/1 3 A4

-Xl-

Hatriuiihjdrogensulfit to submit before the soap treatment ta, Remove any loosely adhering dye from the surface of the textile material, see below.

The styryl dyes of the invention have an excellent one Affinity and excellent build-up properties on synthetic Textilmatorialiqn, so that it is possible to add deep dyes obtain. The resulting dyeings, whose hue ranges from greenish yellow to orange, have excellent fastness to light, wet treatments and especially dry ones Heat treatments, «ie ζ« Β. Iron.

The invention is illustrated in more detail by the following examples, in which all parts and percentages are expressed by weight

example 1

Am mixture of 4.9 parts of 3-methoxy-4- (ß-hydroxyäthylajnino) - u>, "" -dlcyanostyrol, 80 parts of toluene and 2.5 parts of phenyl isocyanate for 4 hours at 100 ⁰ C is stirred. The mixture is then cooled to 15 ° C, and the precipitated S-metho ^ y - * - (ß-Cphenylcarbamoyloxy ^ äthylaminoJ-aj ^^ icyanostyrene is filtered off and dried. The dye obtained in this way has a melting point of ⁰

1098 3 9/1344

- 12 -

If / in an aqueous medium that is pearled, then the color thus obtained dye polyes te! textile material ie η in splendid yellow shades with excellent authenticity properties

The i-methoxy-4- (3-hydroxyethylamino) -c >>, <>> - dicyanoatyrene, which was used in the above example, was prepared as follows: A mixture of 84 parts of H- (3-hydroxyethyl) -o -anisidin and 250 parts konsentrierter aqueous Sal "acid was cooled to 5 ⁰ O. 40 parts of a 37 £ lgen aqueous solution of formaldehyde was added over 30 minutes and the Qeaisoh was stirred for 20 hours at 0 to 5 ⁰ C. 1,000 parts of water "125 parts of concentrated aqueous Salssäure and 130 parts Hatriumm ~ were nltrobenzoleulfonat added, the mixture was warmed to 20 ⁰ C, and while Λ hour, 123 '" rush finely divided iron added, the temperature while at 70 ⁰ C increased The mixture was stirred for 4 hours and the orange precipitate was then filtered off. The solid was dissolved in 900 parts of water by adding sodium carbonate, the solution was filtered, 50 parts of 40% aqueous solution of sodium hydroxide were added to the filtrate, which The resulting mixture was filtered off, the aldehyde was separated off by extraction with chloroform, which was then removed by distillation, the aldehyde remaining in the form of a solid.

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- 13 -

A mixture of 19.5 parts of this aldehyde, 6.6 parts dinitrile, 40 parts of ethanol and 0.1 part of piperidine was "Stirred under boiling in a reflux condenser for 30 minutes" DeB Oeedech was then cooled and the precipitated solid was filtered off and dried.

Example 2

3t5 parts of benzoyl chloride are gradually added to a solution of iron 4.9 parts of 3J-llethoxy-4- (ß-hydroxyethylomino) - <^ _l u * -diCjanostyrol in 30 parts of pyridine at 20 ⁰ C, and the Geaisch is 5 hours at 20 Stirred to 25 ^{0 C.} The resulting solution is poured into water, and the precipitated 3-kethoiy-4- [e- (benaioyloxy) -äthylamino7-io, ai-dlcyano8tyrol is filtered off, washed with water and dried. This dye melts at ⁰

If it is diapered in an aqueous medium, then it stains the dye textile materials made of aromatic polyester in magnificent yellow tones with excellent Bechtheltechaften.

Example 3

A mixture of 28.5 parts of 4- £ 3- (Hionoxy) -äthylaminoJ-5 - «« taoxy ~ 2-ethylbyn * aldehyde, 6.6 parts of malononitrile, 40 parts

! 0 fl H j ^c i

Ethanol and 0.1 part of piperidine is boiled under one The reflux condenser was stirred for 30 minutes. The mixture is then cooled, and the precipitated Perbetoff is filtered off and dried·

If it is dispersed in a tarry medium, it stains The color and text received are made of aromatic materials Polyesters in gorgeous yellow tones with excellent visual properties

The aldehyde used in this example was obtained as follows:

A mixture of 25.7 parts of lf- (Ö-phenoxyethyl) -2-methoxy-5 methylaniline, 20 parts of hexamethylenetetramine and 15 parts Ethanol was stirred at the boil under a reflux condenser for 15 minutes x 15 parts of a mixture of equal parts Formic acid and acetic acid were then added, the mixture was stirred at the boil for 2 1/2 hours, during which 30 parts of the same acid mixture were gradually added. The mixture was then stirred at the boil for a further 2 1/2 hours. Hu The mixture was then poured into 200 parts of a 1.8% aqueous A solution of hydrochloric acid was poured in, the mixture was stirred for 4 hours, the aldehyde, which separated out as oil, was extracted from chloroform, and the chloroform was then extracted from the extract removed by distillation.

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Example. 4th

Instead of the 28.5 parts of the aldehyde used in Example 3, 52.9 parts of 4- £ ß- (a ⁱ -Pheno3tyäthoxy) -ätnylaminoJ-5-methoxy-2-methylbenzaldehyde are used, whereby a similar dye is obtained.

The aldehyde in this example was prepared by the method described in the last paragraph of Example 3, but starting from 30.1 parts of S- | ß- (ß ^f -phenoxyethoxy) ethylJ * 2- «ethoxy-5-methylaniline.

example $

Instead of the 4.9 parts of 5-ethoxy-4- (ß-hydroxyäthylanino) -co »wdicyanostyrene, which were used in Example 1, 5.1 parts of 3-methoxy-4- (ß-hydro3cyiäthylaoino) -6-ethyl- co, cj-dicyanoatyrene used. The dye thus obtained melts at 100 ⁰ C. When it is diepergiert in an aqueous medium, then stained Textilmateriallen of aromatic polyesters in magnificently yellow shades with excellent fastness properties.

The styrene derivative used as the starting material in this example was replaced by the method described in the last two paragraphs of

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Example 1 described method produced old, except that the N- (ß-hydroxyethyl) -o-aniBidin 5-B -2-methoxy-»ethylaniline was replaced by a ftquiva lente amount of N- (ß-hydroxyethyl).

Example 6

Instead of 3.5 parts of benzoyl chloride used in Example 2, 5 »0 parts of 4-Carbomethoxybenzoyl chloride or 4.2 parts Fhenoxyacetylchlorid used, with similar dyes are obtained which melt and 124 ⁰ C at the 170th

Example 7

Instead of the 4.9 parts of 3-methoxy-4- (ß-hydroacyättiyleaino) - * e, a> -dlcyanostyrene, which were used in Example 1, 5.6 parts of 3-methoxy-4- (ß-hydroxyäthylamino) - 6-chloro- <*, «»> -dicyanostyrene used, whereby a similar dye is obtained (melting point 194 ⁰ C).

The styrene derivative used as the starting material in this example was replaced by that described in the last two paragraphs of Example 1 obtained method described, with the difference that the N ~ (ß-hydroxyethyl) -o-anieidin by an equivalent Amount of N- (ß-hydroxyethyl) -2-methoxy-5-chloroaniline was replaced

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Example 8

5 | 0 parts of ^ -Carbomethoxybenzoylchlorid are gradually added to a solution of 5.1 parts of 3-methoxy-4- (β-hydroxyethylamino) - »6-methyl-coitAJ-dicyanostyrene in 20 parts of? Yridine at 20 ⁰ C, and that The mixture is stirred for 5 hours at 20 to 25 ^° C. * The solution is poured into water, and the precipitated Λ 3-methoxy-4 fß- (4 '-carbomethoxybenzoyloxy) -äthylaminoj -6- methyl- (jj, c <j -dicyanostyrol is filtered off, / ater washed with V and dried. The dyestuff melts at 205 ⁰ C.

When dispersed in an aqueous medium, it stains the dye polyester textile materials in gorgeous yellow Color shades with excellent fastness properties.

Instead of the 5.0 parts 4-carbomethoxybenzoyl chloride are used equivalent amounts of the following acid chlorides are used, similar dyes being obtained:

(a) 4-JOarbo- (β-methoxyethoxy) J-benzoyl chloride

(b) phenylacetyl chloride
Cc) phenoxyacetyl chloride

Cd) p-nitrophenylacetyl chloride
Ce) o-chlorophenylacetyl chloride
Cf) benzoyl chloride

p-nitrobenzoyl chloride

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(h) m-nitrobenzoyl chloride

(j) p-methoxybenzoyl chloride (k) m-methoxybenzoyl chloride

In the case of the acid chlorides used under (h), (j) and (k) found it necessary to keep the reaction mixture boiling and not to stir at a temperature of 20 to 25 ° C «in order to obtain complete acylation of the starting material.

Example 9

Anate parts of the 4.9 parts of 3-methoxy-4- (u-hydroxyäthylamlno) - «« j, i * 3- · dlcyanostyrene, which were used in Example 1, are 6.0 parts of 3 ~ (o-methoxyethoxy) -4 - (ß ~ hydroxyäthylamino) -6-fflethyl-u>, wüdicyanostyrol used, whereby a similar dye is obtained (Pp ⁰

The styrene compound used as the Auegangematerial in this example was replaced by the in the last two paragraphs of Example 1 obtained method described, with the difference that the N- (fl-hydroxyethyl) -o-anisidine by an equivalent Amount of N- (ß-hydroxyethyl) -2- (ß-methoxyethoxy) -5- «ethylaniline was replaced.

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Example 10

Instead of the 28.5 parts of the aldehyde used in Example 3, an equivalent amount of the following aldehydes is used, similar dyes being obtained:

(a) 4-fß- (ß ^f -> p-chlorophenoxy <-ethoxy) -äthylamino7-5-iftethoxy-2-methylbenzaldehyde

(b) 4- [ß- (o-methylphenoxy) -äthylaminoJ -S-methoxy - ^ - methylbenzaldehyde

(c) 4-. £ ß- (Benzyloxy) -äthylaminoJ -S-methoxy ^ -methylbena-

aldehyde

(d) 4- | ß -. (Phenoxy) ethylaminoJ-5-methoxy-2-bromobene-aldehyde (e) 4- £ β- (Phenoxy ^ -ethylaminoj -2,5-dimethoxybenzaldehyde

(f) 4- £) T- (Phenoxy) -pr opyl aralnoj -5-nie th oxy-2-methylbenz-

aldehyde.

The aldehydes used in this example can be obtained from the corresponding substituted aniline by the procedure described in the last two paragraphs of Example 2 .

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Claims (1)

JEJLSJiJLJL 1. Water-soluble styryl dyes which are free from sulfon on säuregruppeη and have the following formula ι CN Z represents hydrogen, chlorine, bromine, lower alkyl or / Älk ^ xy; R is an optionally substituted lower alkyl radical represents; m is 2 or 2; η is 1 or 2; and Y is an acyloxy, urethane or optionally substituted one Represents alkoxy, aryloxy or aralkoxy group 2. styryl dyes according to claim 1, characterized in that that R represents the methyl radical. 3. styryl dyes according to claim 1 or 2, characterized in that Z represents methyl. 109839/1344 4. styryl dyes according to any one of claims 1 to 3, characterized characterized in that m is equal to 2 5 · Styryl dyes according to one of Claims 1 to 4 »characterized in that η is equal to 1« 6. Styryl dyes according to one of Claims 1 to 5, characterized in that Y is an optionally substituted Phenoxy radical is 7. Styryl dyes according to one of Claims 1 to 5, characterized in that Y is an optionally substituted Benzoyloxy radical represents 8. Process for the preparation of the styryl dyes according to Claim 1, characterized in that an aldehyde of the formula CHO wherein R, Y ₁ Z ₉ m and η have the meanings given in claim 1, reacts with malononitrile * 109839/1344 9 · Process for the production of styryl dyes according to Claim 1, in which Y represents a urethane group, characterized in that an isocyanate is used with a compound of the formula CH wherein R, Z, m and η have the meanings given in claim 1 own, implement 10. A process for the preparation of the styryl dyes according to claim 1, wherein T represents an acyloxy group, thereby ge » indicated that a compound of the formula given in claim 9 is reacted with an acylating agent. ™ 11. The method according to claim 10, characterized in that the acelling agent eats an optionally substituted benzoyl chloride. M. RNCKE. DtPl INO. H. KJHl HPl-INQ. S. SMCÜft 109839/1344